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However, other not-so-known bonding mechanisms also play a crucial role in chemical systems. Particularly important are the charge-shift bond (CSB) and the multicenter bonds, i.e., the electron-rich multicenter bond (ERMB), also known as hypervalent or three-center-four-electron (3c-4e) bond, and the electron-deficient multicenter bond (EDMB), also known as the three-center-two-electron (3c-2e) bond in molecules and, more recently, as the two-center-one-electron (2c-1e) bond in extended solids. We consider that these latter interactions have not yet received the proper attention of the scientific community, even though multicenter interactions were proposed in the early days of Quantum Mechanics. In this work, we aim at providing: (i) a concise historical overview of the two types of multicenter bonds; (ii) a short introduction to the recently proposed unified theory of multicenter bonding (UTMB), which elucidates the origin and mechanisms of formation of both ERMBs and EDMBs; and (iii) an extension of the UTMB to include CSBs, due to the strong relationship between ERMBs and CSBs. We hope that the integrated perspective of chemical bonding, the heartland of chemistry, offered by the UTMB (beyond traditional and historical assumptions) will help researchers to understand materials properties and will provide a framework allowing the development of advanced materials for enhanced technological applications.<\/jats:p>","DOI":"10.3390\/molecules31010082","type":"journal-article","created":{"date-parts":[[2025,12,24]],"date-time":"2025-12-24T16:41:19Z","timestamp":1766594479000},"page":"82","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":4,"title":["Introduction and Extension of the Unified Theory of Multicenter Bonding: The Role of the Charge-Shift Bonding"],"prefix":"10.3390","volume":"31","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-3926-1705","authenticated-orcid":false,"given":"Francisco Javier","family":"Manj\u00f3n","sequence":"first","affiliation":[{"name":"Instituto de Dise\u00f1o para la Fabricaci\u00f3n y Producci\u00f3n Automatizada, MALTA Consolider Team, Universitat Polit\u00e8cnica de Val\u00e8ncia, 46022 Valencia, Spain"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-1411-8299","authenticated-orcid":false,"given":"Hussien H.","family":"Osman","sequence":"additional","affiliation":[{"name":"Instituto de Dise\u00f1o para la Fabricaci\u00f3n y Producci\u00f3n Automatizada, MALTA Consolider Team, Universitat Polit\u00e8cnica de Val\u00e8ncia, 46022 Valencia, Spain"},{"name":"Instituto de Ciencia de los Materiales de la Universitat de Val\u00e8ncia, MALTA Consolider Team, Universitat de Val\u00e8ncia, 46100 Valencia, Spain"},{"name":"Chemistry Department, Faculty of Science, Helwan University, Cairo 11795, Egypt"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-2798-6178","authenticated-orcid":false,"given":"\u00c1lvaro","family":"Lobato","sequence":"additional","affiliation":[{"name":"Departamento de Qu\u00edmica F\u00edsica, MALTA Consolider Team, Universidad Complutense de Madrid, 28040 Madrid, Spain"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-7237-4720","authenticated-orcid":false,"given":"Fernando","family":"Izquierdo-Ruiz","sequence":"additional","affiliation":[{"name":"Departamento de Qu\u00edmica F\u00edsica, MALTA Consolider Team, Universidad Complutense de Madrid, 28040 Madrid, Spain"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-0956-3195","authenticated-orcid":false,"given":"Enrico","family":"Bandiello","sequence":"additional","affiliation":[{"name":"Instituto de Dise\u00f1o para la Fabricaci\u00f3n y Producci\u00f3n Automatizada, MALTA Consolider Team, Universitat Polit\u00e8cnica de Val\u00e8ncia, 46022 Valencia, Spain"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-6516-4303","authenticated-orcid":false,"given":"Samuel","family":"Gallego-Parra","sequence":"additional","affiliation":[{"name":"Instituto de Dise\u00f1o para la Fabricaci\u00f3n y Producci\u00f3n Automatizada, MALTA Consolider Team, Universitat Polit\u00e8cnica de Val\u00e8ncia, 46022 Valencia, Spain"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-6651-9858","authenticated-orcid":false,"given":"\u00c1ngel","family":"Vegas","sequence":"additional","affiliation":[{"name":"Independent Researcher, Calle Espinarejo 1, 28400 Collado Villalba, Spain"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-9780-7542","authenticated-orcid":false,"given":"Matteo","family":"Savastano","sequence":"additional","affiliation":[{"name":"Department of Human Sciences for the Promotion of Quality of Life, University San Raffaele Roma, Via di Val Cannuta 247, 00166 Rome, Italy"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-3347-6518","authenticated-orcid":false,"given":"Alfonso","family":"Mu\u00f1oz","sequence":"additional","affiliation":[{"name":"Departamento de F\u00edsica, MALTA Consolider Team, Universidad de La Laguna, 38205 La Laguna, Spain"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"1968","published-online":{"date-parts":[[2025,12,24]]},"reference":[{"key":"ref_1","unstructured":"Hoffmann, R. Private communication."},{"key":"ref_2","doi-asserted-by":"crossref","first-page":"762","DOI":"10.1021\/ja02261a002","article-title":"The atom and the molecule","volume":"38","author":"Lewis","year":"1916","journal-title":"J. Am. Chem. Soc."},{"key":"ref_3","doi-asserted-by":"crossref","first-page":"1543","DOI":"10.1021\/ja02231a009","article-title":"Isomorphism, Isosterism and Covalence","volume":"41","author":"Langmuir","year":"1919","journal-title":"J. Am. Chem. Soc."},{"key":"ref_4","doi-asserted-by":"crossref","first-page":"10447","DOI":"10.1039\/D4TC00604F","article-title":"Electron-deficient multicenter bonding in pnictogens and chalcogens: Mechanism of formation","volume":"12","author":"Osman","year":"2024","journal-title":"J. Mater. Chem. C"},{"key":"ref_5","doi-asserted-by":"crossref","first-page":"3774\u22123803","DOI":"10.1039\/D4TC04441J","article-title":"A unified theory of electron-rich and electron-deficient multicenter bonds in molecules and solids: A change of paradigms","volume":"13","author":"Osman","year":"2025","journal-title":"J. Mater. Chem. C"},{"key":"ref_6","doi-asserted-by":"crossref","first-page":"51\u221261","DOI":"10.1002\/jcc.20517","article-title":"The Lewis legacy: The chemical bond\u2014A territory and heartland of chemistry","volume":"28","author":"Shaik","year":"2007","journal-title":"J. Comput. Chem."},{"key":"ref_7","doi-asserted-by":"crossref","unstructured":"Gatti, C., and Raty, J.-Y. (2025). Comment on \u2018Chemical bonding in phase-change chalcogenides\u2019. J. Phys. Condens. Matter., 37.","DOI":"10.1088\/1361-648X\/adec2c"},{"key":"ref_8","doi-asserted-by":"crossref","first-page":"1315","DOI":"10.1016\/j.ccr.2007.07.007","article-title":"Fifty years of the VSEPR model","volume":"252","author":"Gillespie","year":"2008","journal-title":"Coord. Chem. Rev."},{"key":"ref_9","doi-asserted-by":"crossref","unstructured":"Manj\u00f3n, F.J., Osman, H.H., Savastano, M., and Vegas, \u00c1. (2024). Electron-deficient multicenter bonding in phase change materials: A chance for reconciliation. Materials, 17.","DOI":"10.3390\/ma17122840"},{"key":"ref_10","doi-asserted-by":"crossref","unstructured":"Osman, H.H., and Manj\u00f3n, F.J. (2025). Chemical Bonding in Dense AIVXVI and A2VX3VI Chalcogenides: Electron-Deficient Multicenter Bonds in Electron-Rich Elements. J. Mat. Chem. C, 13.","DOI":"10.26434\/chemrxiv-2025-47hpc"},{"key":"ref_11","doi-asserted-by":"crossref","unstructured":"Garcia-Sanchez, T., Cuenca-Gotor, V.P., Osman, H.H., Mu\u00f1oz, A., Rodr\u00edguez-Hern\u00e1ndez, P., Sans, J.A., Gallego-Parra, S., Popescu, C., Oeckler, O., and Errandonea, D. (2025). Structural, vibrational, and electrical study of the topological insulator PbBi2Te4 at high pressure. J. Alloys Comp., 1010.","DOI":"10.1016\/j.jallcom.2024.177010"},{"key":"ref_12","doi-asserted-by":"crossref","unstructured":"Errandonea, D., Osman, H.H.H., Turnbull, R., Diaz-Anichtchenko, D., Liang, A., Sanchez-Martin, J., Popescu, C., Jiang, D., Song, H., and Wang, Y. (2024). Pressure-induced hypercoordination of iodine and dimerization of I2O6H in strontium di-iodate hydrogen-iodate (Sr(IO3)2HIO3). Mater. Today Adv., 22.","DOI":"10.1016\/j.mtadv.2024.100495"},{"key":"ref_13","doi-asserted-by":"crossref","unstructured":"Errandonea, D., Turnbull, R., Osman, H.H.H., Hebboul, Z., Botella, P., Bura, N., Zhang, P., Rodrigo-Ram\u00f3n, J.L., S\u00e1nchez-Mart\u00edn, J., and Popescu, C. (2025). Effects of Compression on the Local Iodine Environment in Dipotassium Zinc Tetraiodate(V) Dihydrate K2Zn(IO3)4\u00b72H2O. Inorg. Chem., 64.","DOI":"10.1021\/acs.inorgchem.5c00911"},{"key":"ref_14","doi-asserted-by":"crossref","unstructured":"Bandiello, E., Osman, H.H., Sans, J.A., Rodr\u00edguez-Hern\u00e1ndez, P., Mu\u00f1oz, A., Gonz\u00e1lez-Platas, J., Popescu, C., Greenberg, E., Prakapenka, V., and Drasar, C. (2024). Rashba asymmetric topological insulator BiTeCl under compression: Equation of state, vibrational features and electronic properties. J. Mater. Chem. C, 12.","DOI":"10.1039\/D4TC03027C"},{"key":"ref_15","doi-asserted-by":"crossref","first-page":"4187\u22124202","DOI":"10.1021\/acs.chemmater.5c00877","article-title":"Unconventional Electron-Deficient Multicenter Bonds in AIO3 Perovskites","volume":"37","author":"Osman","year":"2025","journal-title":"Chem. Mater."},{"key":"ref_16","doi-asserted-by":"crossref","unstructured":"Savastano, M., Osman, H.H., Vegas, \u00c1., and Manj\u00f3n, F.J. (2024). Rethinking polyiodides: The role of electron-deficient multicenter bonds. Chem. Commun., 60.","DOI":"10.26434\/chemrxiv-2024-5w7wp"},{"key":"ref_17","doi-asserted-by":"crossref","unstructured":"Bandiello, E., Lobato, \u00c1., Izquierdo, F., Osman, H.H., Mu\u00f1oz, A., Rodr\u00edguez-Hern\u00e1ndez, P., and Manj\u00f3n, F.J. (2025). From Polyanions to Infinite Chains: Chemical Bonding Evolution in AX3 Polyhalides under Pressure. J. Mater. Chem. C, 13.","DOI":"10.26434\/chemrxiv-2025-gdx2s"},{"key":"ref_18","doi-asserted-by":"crossref","unstructured":"Sulli, M., Bianchi, A., Bazzicalupi, C., and Savastano, M. (2025). Incommensurately modulated sodium polyiodide crystal structure discloses unconventional 1D iodine chains. Cell Rep. Phys. Sci., 6.","DOI":"10.1016\/j.xcrp.2025.102925"},{"key":"ref_19","doi-asserted-by":"crossref","unstructured":"Osman, H.H., Mu\u00f1oz, A., Segura, A., and Manj\u00f3n, F.J. (2025). Can metallic bonding exhibit multicenter character?. ChemRxiv.","DOI":"10.26434\/chemrxiv-2025-9rf54"},{"key":"ref_20","doi-asserted-by":"crossref","unstructured":"Wuttig, M., Sch\u00f6n, C.-F., Kim, D., Golub, P., Gatti, C., Raty, J.-Y., Kooi, B.J., Mart\u00edn Pend\u00e1s, \u00c1., Arora, R., and Waghmare, U. (2023). Metavalent or hypervalent bonding: Is there a chance for reconciliation?. Adv. Sci., 11.","DOI":"10.1002\/advs.202308578"},{"key":"ref_21","doi-asserted-by":"crossref","first-page":"1","DOI":"10.1107\/S0365110X64000019","article-title":"The crystal structures of semiconductors and a general valence rule","volume":"17","author":"Pearson","year":"1964","journal-title":"Acta Cryst."},{"key":"ref_22","doi-asserted-by":"crossref","first-page":"5529","DOI":"10.1063\/1.1501133","article-title":"From weak to strong interactions: A comprehensive analysis of the topological and energetic properties of the electron density distribution involving systems","volume":"117","author":"Espinosa","year":"2002","journal-title":"J. Chem. Phys."},{"key":"ref_23","doi-asserted-by":"crossref","first-page":"565","DOI":"10.1021\/ar010054t","article-title":"Hydrogen Bridges in Crystal Engineering:\u2009 Interactions without Borders","volume":"35","author":"Desiraju","year":"2002","journal-title":"Acc. Chem. Res."},{"key":"ref_24","doi-asserted-by":"crossref","first-page":"624","DOI":"10.1107\/S0108768109026767","article-title":"Topological properties of hydrogen bonds and covalent bonds from charge densities obtained by the maximum entropy method (MEM)","volume":"6","author":"Netzela","year":"2009","journal-title":"Acta Cryst. B"},{"key":"ref_25","doi-asserted-by":"crossref","first-page":"6358","DOI":"10.1002\/chem.200500265","article-title":"Charge-shift bonding\u2014A class of electron-pair bonds that emerges from valence bond theory and is supported by the electron localization function approach","volume":"11","author":"Shaik","year":"2005","journal-title":"Chem.\u2014Eur. J."},{"key":"ref_26","first-page":"759","article-title":"Zur deutung der molekelspektren","volume":"51","author":"Hund","year":"1928","journal-title":"Iv. Z. Phys."},{"key":"ref_27","doi-asserted-by":"crossref","first-page":"555","DOI":"10.1007\/BF01339455","article-title":"\u00dcber die quantenmechanik der elektronen in kristallgittern","volume":"52","author":"Bloch","year":"1929","journal-title":"Z. Phys."},{"key":"ref_28","doi-asserted-by":"crossref","first-page":"204","DOI":"10.1007\/BF01339530","article-title":"Quanstentheoretische beitr\u00e4ge zum benzolproblem: II. quantentheorie der induzierten polarit\u00e4ten","volume":"70","year":"1931","journal-title":"Z. Phys."},{"key":"ref_29","doi-asserted-by":"crossref","first-page":"1327","DOI":"10.1021\/ja01198a028","article-title":"Electron Deficient Compounds1","volume":"69","author":"Rundle","year":"1947","journal-title":"J. Am. Chem. Soc."},{"key":"ref_30","doi-asserted-by":"crossref","first-page":"671","DOI":"10.1063\/1.1747367","article-title":"Electron Deficient Compounds. II. Relative Energies of \u201cHalf-Bonds\u201d","volume":"17","author":"Rundle","year":"1949","journal-title":"J. Chem. Phys."},{"key":"ref_31","doi-asserted-by":"crossref","first-page":"45","DOI":"10.1021\/j150547a010","article-title":"Electron deficient compounds","volume":"61","author":"Rundle","year":"1957","journal-title":"J. Phys. Chem."},{"key":"ref_32","doi-asserted-by":"crossref","first-page":"121","DOI":"10.1039\/qr9571100121","article-title":"The structures of electron-deficient molecules","volume":"11","year":"1957","journal-title":"Q. Rev. Chem. Soc."},{"key":"ref_33","doi-asserted-by":"crossref","first-page":"4321","DOI":"10.1021\/ja01153a086","article-title":"The Structure of Tetramethylammonium Pentaiodide1,1a","volume":"73","author":"Hach","year":"1951","journal-title":"J. Am. Chem. Soc."},{"key":"ref_34","doi-asserted-by":"crossref","first-page":"446","DOI":"10.1063\/1.1748245","article-title":"The bonding of trihalide and bifluoride ions by the molecular orbital method","volume":"19","author":"Pimentel","year":"1951","journal-title":"J. Chem. Phys."},{"key":"ref_35","doi-asserted-by":"crossref","first-page":"54","DOI":"10.1002\/anie.196900541","article-title":"The chemistry of hypervalent molecules","volume":"8","author":"Musher","year":"1969","journal-title":"Angew. Chem. Int. Ed. Engl."},{"key":"ref_36","doi-asserted-by":"crossref","unstructured":"Wade, K. (1971). Electron Deficient Compounds, Nelson.","DOI":"10.1007\/978-1-4684-6054-4"},{"key":"ref_37","doi-asserted-by":"crossref","unstructured":"Harcourt, R.D. (1982). Qualitative Valence-Bond Descriptions of Electron-Rich Molecules: Pauling \u201c3-Electron Bonds\u201d and \u201cIncreased-Valence\u201d Theory, Springer.","DOI":"10.1007\/978-3-642-93216-8"},{"key":"ref_38","doi-asserted-by":"crossref","first-page":"2408","DOI":"10.1002\/1521-3773(20000717)39:14<2408::AID-ANIE2408>3.0.CO;2-U","article-title":"Hypervalent bonding in one, two, and three dimensions: Extending the Zintl\u2013Klemm concept to nonclassical electron-rich networks","volume":"39","author":"Papoian","year":"2000","journal-title":"Angew. Chem. Int. Ed."},{"key":"ref_39","doi-asserted-by":"crossref","first-page":"7161","DOI":"10.1021\/ic400772u","article-title":"Hypervalent Compounds as Ligands: I3-Anion Adducts with Transition Metal Pentacarbonyls","volume":"52","author":"Rogachev","year":"2013","journal-title":"Inorg. Chem."},{"key":"ref_40","doi-asserted-by":"crossref","unstructured":"Harcourt, R.D. (2016). Bonding in Electron-Rich Molecules, Springer International Publishing.","DOI":"10.1007\/978-3-319-16676-6"},{"key":"ref_41","unstructured":"International Union of Pure and Applied Chemistry (IUPAC) (2025). IUPAC\u2014Lewis Acid (L03508), IUPAC."},{"key":"ref_42","unstructured":"International Union of Pure and Applied Chemistry (IUPAC) (2025). IUPAC\u2014Lewis Base (L03511), IUPAC."},{"key":"ref_43","unstructured":"International Union of Pure and Applied Chemistry (IUPAC) (2025). IUPAC\u2014Lewis Adduct (L03510), IUPAC."},{"key":"ref_44","doi-asserted-by":"crossref","unstructured":"Gutmann, V. (1978). The Donor-Acceptor Approach to Molecular Interactions, Springer.","DOI":"10.1007\/978-1-4615-8825-2"},{"key":"ref_45","doi-asserted-by":"crossref","first-page":"207","DOI":"10.1016\/S0010-8545(00)80274-X","article-title":"Empirical approach to molecular interactions","volume":"15","author":"Gutmann","year":"1975","journal-title":"Coord. Chem. Rev."},{"key":"ref_46","doi-asserted-by":"crossref","first-page":"1047","DOI":"10.1126\/science.196.4294.1047","article-title":"The Boranes and their Relatives","volume":"196","author":"Lipscomb","year":"1977","journal-title":"Science"},{"key":"ref_47","doi-asserted-by":"crossref","first-page":"2653","DOI":"10.1103\/PhysRevB.33.2653","article-title":"Theory of the multicenter bond","volume":"33","author":"Harrison","year":"1986","journal-title":"Phys. Rev. B"},{"key":"ref_48","doi-asserted-by":"crossref","first-page":"3","DOI":"10.1016\/S0022-2860(02)00231-4","article-title":"The synaptic order: A key concept to understand multicenter bonding","volume":"614","author":"Silvi","year":"2002","journal-title":"J. Mol. Struct."},{"key":"ref_49","doi-asserted-by":"crossref","first-page":"419","DOI":"10.1007\/s00214-004-0597-9","article-title":"Multicenter bonding and the structure of electron-rich molecules. Model of three-center four-electron bonding reconsidered","volume":"112","author":"Ponec","year":"2004","journal-title":"Theor. Chem. Acc."},{"key":"ref_50","doi-asserted-by":"crossref","first-page":"2514","DOI":"10.1021\/ar5001555","article-title":"Halogen Bonds in Crystal Engineering: Like Hydrogen Bonds yet Different","volume":"47","author":"Mukherjee","year":"2014","journal-title":"Acc. Chem. Res."},{"key":"ref_51","unstructured":"Vegas, \u00c1. (2018). Structural Models of Inorganic Crystals, Universitat Polit\u00e8cnica de Val\u00e8ncia. Chapter 15."},{"key":"ref_52","doi-asserted-by":"crossref","first-page":"163","DOI":"10.1107\/S2052519213001048","article-title":"Isoelectronic and isolobal O, CH2, CH3+ and BH3 as electron pairs; similarities between molecular and solid-state chemistry","volume":"69","author":"Vegas","year":"2013","journal-title":"Acta Crystallogr."},{"key":"ref_53","doi-asserted-by":"crossref","first-page":"347","DOI":"10.1038\/s41586-024-07965-1","article-title":"Direct evidence for a carbon\u2013carbon one-electron \u03c3-bond","volume":"634","author":"Shimajiri","year":"2024","journal-title":"Nature"},{"key":"ref_54","unstructured":"Grimes, R.N. (2016). Carboranes, Academic Press. [3rd ed.]."},{"key":"ref_55","doi-asserted-by":"crossref","first-page":"1517","DOI":"10.1002\/(SICI)1096-987X(19991115)20:14<1517::AID-JCC4>3.0.CO;2-#","article-title":"Topological analysis of electron density in depleted homopolar chemical bonds","volume":"20","author":"Llusar","year":"1999","journal-title":"J. Comput. Chem."},{"key":"ref_56","doi-asserted-by":"crossref","first-page":"10150","DOI":"10.1021\/jp304420c","article-title":"Two-Center Two-Electron Covalent Bonds with Deficient Bonding Densities","volume":"116","author":"Yang","year":"2012","journal-title":"J. Phys. Chem. A"},{"key":"ref_57","doi-asserted-by":"crossref","first-page":"169","DOI":"10.1007\/430_2015_179","article-title":"New Landscape of Electron-Pair Bonding Covalent, Ionic, and Charge-Shift Bonds","volume":"170","author":"Shaik","year":"2015","journal-title":"the Chemical Bond II. Structure and Bonding"},{"key":"ref_58","doi-asserted-by":"crossref","first-page":"996","DOI":"10.1002\/ange.201910085","article-title":"Charge-shift bonding: A new and unique form of bonding","volume":"132","author":"Shaik","year":"2020","journal-title":"Angew. Chem. Int. Ed."},{"key":"ref_59","doi-asserted-by":"crossref","unstructured":"Wuttig, M., Deringer, V.L., Gonze, X., Bichara, C., and Raty, J.-Y. (2018). Incipient metals: Functional materials with a unique bonding mechanism. Adv. Mater., 30.","DOI":"10.1002\/adma.201803777"},{"key":"ref_60","doi-asserted-by":"crossref","unstructured":"Raty, J.-Y., Schumacher, M., Golub, P., Deringer, V.L., Gatti, C., and Wuttig, M. (2019). A quantum-mechanical map for bonding and properties in solids. Adv. Mater., 31.","DOI":"10.1002\/adma.201806280"},{"key":"ref_61","doi-asserted-by":"crossref","unstructured":"Cheng, Y., Cojocaru-Mir\u00e9din, O., Keutgen, J., Yu, Y., K\u00fcpers, M., Schumacher, M., Golub, P., Raty, J.-Y., Dronskowski, R., and Wuttig, M. (2019). Understanding the Structure and Properties of Sesqui-Chalcogenides (i.e., V2VI3 or Pn2Ch3 (Pn = Pnictogen, Ch = Chalcogen) Compounds) from a Bonding Perspective. Adv. Mater., 31.","DOI":"10.1002\/adma.201904316"},{"key":"ref_62","doi-asserted-by":"crossref","unstructured":"Wuttig, M., Sch\u00f6n, C.-F., Schumacher, M., Robertson, J., Golub, P., Bousquet, E., Gatti, C., and Raty, J. (2022). Halide perovskites: Advanced photovoltaic materials empowered by a unique bonding mechanism. Adv. Funct. Mater., 32.","DOI":"10.1002\/adfm.202110166"},{"key":"ref_63","doi-asserted-by":"crossref","unstructured":"Lee, T.H., and Elliott, S.R. (2020). Chemical bonding in chalcogenides: The concept of multicenter hyperbonding. Adv. Mater., 32.","DOI":"10.1002\/adma.202000340"},{"key":"ref_64","doi-asserted-by":"crossref","unstructured":"Lee, T.H., and Elliott, S.R. (2021). Multi-Center Hyperbonding in Phase-Change Materials. Phys. Status Solidi RRL, 15.","DOI":"10.1002\/pssr.202000516"},{"key":"ref_65","doi-asserted-by":"crossref","first-page":"7959","DOI":"10.1021\/acs.jpcc.1c00718","article-title":"Crystal orbital bond index: Covalent bond orders in solids","volume":"125","author":"Ertural","year":"2021","journal-title":"J. Phys. Chem. C"},{"key":"ref_66","doi-asserted-by":"crossref","unstructured":"Hempelmann, J., M\u00fcller, P.C., Konze, P.M., Stoffel, R.P., Steinberg, S., and Dronskowski, R. (2021). Long-Range Forces in Rock-Salt-Type Tellurides and How they Mirror the Underlying Chemical Bonding. Adv. Mater., 33.","DOI":"10.1002\/adma.202100163"},{"key":"ref_67","doi-asserted-by":"crossref","unstructured":"Lee, T.H., and Elliott, S.R. (2022). Hypervalency in amorphous chalcogenides. Nat. Commun., 13.","DOI":"10.1038\/s41467-022-29054-5"},{"key":"ref_68","doi-asserted-by":"crossref","unstructured":"Hempelmann, J., M\u00fcller, P.C., Ertural, C., and Dronskowski, R. (2022). The Orbital Origins of Chemical Bonding in Ge\u2212Sb\u2212Te Phase-Change Materials. Angew. Chem. Int. Ed., 61.","DOI":"10.1002\/anie.202115778"},{"key":"ref_69","doi-asserted-by":"crossref","unstructured":"M\u00fcller, P.C., Elliott, S.R., Dronskowski, R., and Jones, R.O. (2024). Chemical bonding in phase-change chalcogenides. J. Phys. Condens. Matter, 36.","DOI":"10.1088\/1361-648X\/ad46d6"},{"key":"ref_70","doi-asserted-by":"crossref","first-page":"417","DOI":"10.1038\/nchem.1619","article-title":"The essential role of charge-shift bonding in hypervalent prototype XeF2","volume":"5","author":"Hiberty","year":"2013","journal-title":"Nat. Chem."},{"key":"ref_71","doi-asserted-by":"crossref","first-page":"9643","DOI":"10.1002\/chem.201402755","article-title":"A Valence Bond Model for Electron-Rich Hypervalent Species: Application to SFn (n = 1, 2, 4), PF5, and ClF3","volume":"20","author":"Ribeyre","year":"2014","journal-title":"Chem. Eur. J."},{"key":"ref_72","doi-asserted-by":"crossref","first-page":"764","DOI":"10.1063\/1.1749590","article-title":"On the possibility of a metallic modification of hydrogen","volume":"3","author":"Wigner","year":"1935","journal-title":"J. Chem. Phys."},{"key":"ref_73","doi-asserted-by":"crossref","first-page":"345","DOI":"10.1038\/340345a0","article-title":"Metallic hydrogen and beyond","volume":"340","author":"Aschroft","year":"1989","journal-title":"Nature"},{"key":"ref_74","doi-asserted-by":"crossref","first-page":"3620","DOI":"10.1002\/anie.200602485","article-title":"The Chemical Imagination at Work in Very Tight Places","volume":"46","author":"Grochala","year":"2007","journal-title":"Angew. Chem. Int. Ed."},{"key":"ref_75","doi-asserted-by":"crossref","unstructured":"Marqu\u00e9s, M., McMahon, M.I., Gregoryanz, E., Hanfland, M., Guillaume, C.L., Pickard, C.J., Ackland, G.J., and Nelmes, R.J. (2011). Crystal Structures of Dense Lithium: A Metal-Semiconductor-Metal Transition. Phys. Rev. Lett., 106.","DOI":"10.1103\/PhysRevLett.106.095502"},{"key":"ref_76","doi-asserted-by":"crossref","first-page":"338","DOI":"10.1107\/S0108768110013200","article-title":"Towards a generalized vision of oxides: Disclosing the role of cations and anions in determining unit-cell dimensions","volume":"B66","author":"Vegas","year":"2010","journal-title":"Acta Cryst."},{"key":"ref_77","first-page":"5281\u22125291","article-title":"Generalized Stress-Redox Equivalence: A Chemical Link between Pressure and Electronegativity","volume":"59","author":"Lobato","year":"2020","journal-title":"Inorganic Crystals. Inorg. Chem."},{"key":"ref_78","doi-asserted-by":"crossref","first-page":"4271\u22124285","DOI":"10.1063\/1.474769","article-title":"Properties of atoms in molecules: Atoms under pressure","volume":"107","author":"Bader","year":"1997","journal-title":"J. Chem. Phys."},{"key":"ref_79","doi-asserted-by":"crossref","unstructured":"Bader, R.F.W. (1990). Atoms in Molecules: A Quantum Theory, Clarendon Press.","DOI":"10.1093\/oso\/9780198551683.001.0001"},{"key":"ref_80","doi-asserted-by":"crossref","first-page":"819","DOI":"10.1007\/s00706-005-0307-x","article-title":"The quantum mechanical basis of conceptual chemistry","volume":"136","author":"Bader","year":"2005","journal-title":"Monatshefte Chem."},{"key":"ref_81","doi-asserted-by":"crossref","first-page":"5535","DOI":"10.1103\/PhysRevB.41.5535","article-title":"Rhombohedral to simple-cubic phase transition in arsenic under pressure","volume":"41","author":"Beister","year":"1990","journal-title":"Phys. Rev. B"},{"key":"ref_82","doi-asserted-by":"crossref","first-page":"319","DOI":"10.1080\/08957950412331281057","article-title":"High-pressure structural studies of group-15 elements","volume":"24","author":"Degtyareva","year":"2004","journal-title":"High Press. Res."},{"key":"ref_83","doi-asserted-by":"crossref","first-page":"14135","DOI":"10.1002\/anie.201708368","article-title":"Interlayer bond formation in black phosphorus at high pressure","volume":"56","author":"Scelta","year":"2017","journal-title":"Angew. Chem. Int. Ed."},{"key":"ref_84","doi-asserted-by":"crossref","first-page":"223","DOI":"10.1002\/pssb.2220560120","article-title":"Hydrostatic pressure dependence of first-order Raman frequencies in Se and Te","volume":"56","author":"Richter","year":"1973","journal-title":"Phys. Status Solidi B"},{"key":"ref_85","doi-asserted-by":"crossref","first-page":"17","DOI":"10.1143\/JPSJS.76SA.17","article-title":"Pressure-induced phase transitions of trigonal, rhombohedral, orthorhombic, and \u03b1-monoclinic selenium","volume":"76","author":"Masaharu","year":"2007","journal-title":"J. Phys. Soc."},{"key":"ref_86","doi-asserted-by":"crossref","first-page":"4324","DOI":"10.1021\/ja0026962","article-title":"Polyhedral boranes and elemental boron: Direct structural relations and diverse electronic requirements","volume":"123","author":"Jemmis","year":"2001","journal-title":"J. Am. Chem. Soc."},{"key":"ref_87","doi-asserted-by":"crossref","first-page":"1007","DOI":"10.1016\/j.cpc.2013.10.026","article-title":"Critic2: A Program for Real-Space Analysis of Quantum Chemical Interactions in Solids","volume":"185","author":"Johnson","year":"2014","journal-title":"Comput. Phys. Commun."},{"key":"ref_88","doi-asserted-by":"crossref","first-page":"1030","DOI":"10.1002\/jcc.24300","article-title":"LOBSTER: A tool to extract chemical bonding from plane-wave based DFT","volume":"37","author":"Maintz","year":"2016","journal-title":"J. Comput. Chem."},{"key":"ref_89","doi-asserted-by":"crossref","first-page":"1931","DOI":"10.1002\/jcc.26353","article-title":"LOBSTER: Local Orbital Projections, Atomic Charges, and Chemical-bonding Analysis from projector-augmented-wave-based Density-functional Theory","volume":"41","author":"Nelson","year":"2020","journal-title":"J. Comput. Chem."},{"key":"ref_90","doi-asserted-by":"crossref","unstructured":"Patel, N.N., Sunder, M., Garg, A.B., and Poswal, H.K. (2017). Pressure-induced polymorphism in hypervalent CsI3. Phys. Rev. B, 96.","DOI":"10.1103\/PhysRevB.96.174114"},{"key":"ref_91","doi-asserted-by":"crossref","unstructured":"Poreba, T., Racioppi, S., Garbarino, G., Morgenroth, W., and Mezouar, M. (2022). Investigating the Structural Symmetrization of CsI3 at High Pressures through Combined X-ray Diffraction Experiments and Theoretical Analysis. Inorg. Chem., 61.","DOI":"10.1021\/acs.inorgchem.2c01690"},{"key":"ref_92","doi-asserted-by":"crossref","unstructured":"Li, Z.L., Li, Q.J., Li, H.Y., Yue, L., Zhao, D.L., Tian, F., Dong, Q., Zhang, X.T., Jin, X.L., and Zhang, L.J. (2022). Pressure-Tailored Band Engineering for Significant Enhancements in the Photoelectric Performance of CsI3 in the Optical Communication Waveband. Adv. Func. Mater., 32.","DOI":"10.1002\/adfm.202108636"},{"key":"ref_93","doi-asserted-by":"crossref","unstructured":"M\u00fcller, P.C., Elliott, S.R., Dronskowski, R., and Jones, R.O. (2025). Reply to Comment on \u2018Chemical bonding in phase-change chalcogenides\u2019. J. Phys. Condens. Matter., 37.","DOI":"10.1088\/1361-648X\/adec2f"},{"key":"ref_94","doi-asserted-by":"crossref","first-page":"1649","DOI":"10.1021\/cr0204101","article-title":"Synthesis, structure, and bonding in polyiodide and metal iodide\u2212 iodine systems","volume":"103","author":"Svensson","year":"2003","journal-title":"Chem. Rev."},{"key":"ref_95","first-page":"2448\u22122461","article-title":"Linnett is Back: Chemical Bonding through the Lens of Born Maxima","volume":"21","author":"Francisco","year":"2025","journal-title":"J. Chem. Theory Comput."},{"key":"ref_96","unstructured":"Ashcroft, N.W., and Mermin, N.D. (1976). Solid State Physics, Saunders College Publishing."},{"key":"ref_97","doi-asserted-by":"crossref","first-page":"670","DOI":"10.1126\/science.114.2973.670","article-title":"An interpretation of bond lengths and a classification of bonds","volume":"114","author":"Sanderson","year":"1951","journal-title":"Science"},{"key":"ref_98","doi-asserted-by":"crossref","unstructured":"Dong, X., Oganov, A.R., Cui, H., and Wang, H.-T. (2022). Electronegativity and chemical hardness of elements under pressure. Proc. Nat. Acad. Sci. USA, 119.","DOI":"10.1073\/pnas.2117416119"},{"key":"ref_99","unstructured":"Burdett, J.K. (1997). Chemical Bonds: A Dialog, John Wiley and Sons."},{"key":"ref_100","doi-asserted-by":"crossref","unstructured":"Zhang, W., Oganov, A.R., Goncharov, A.F., Zhu, Q., Boulfelfel, S.E., Lyakhov, A.O., Stavrou, E., Somayazulu, M., Prakapenka, V.B., and Konopkova, Z. (2013). Unexpected stable stoichiometries of sodium chlorides. Science, 342.","DOI":"10.1126\/science.1244989"},{"key":"ref_101","doi-asserted-by":"crossref","unstructured":"Zhang, W., Oganov, A.R., Zhu, Q., Lobanov, S.S., Stavrou, E., and Goncharov, A.F. (2016). Stability of numerous novel potassium chlorides at high pressure. Sci. Rep., 6.","DOI":"10.1038\/srep26265"},{"key":"ref_102","doi-asserted-by":"crossref","unstructured":"Yin, Y., Aslandukova, A., Jena, N., Trybel, F., Abrikosov, I.A., Winkler, B., Khandarkhaeva, S., Fedotenko, T., Bykova, E., and Laniel, D. (2023). Unraveling the Bonding Complexity of Polyhalogen Anions: High-Pressure Synthesis of Unpredicted Sodium Chlorides Na2Cl3 and Na4Cl5 and Bromide Na4Br5. J. Am. Chem. Soc. Au, 3.","DOI":"10.1021\/jacsau.3c00090"},{"key":"ref_103","doi-asserted-by":"crossref","first-page":"859\u2212861","DOI":"10.1038\/187859a0","article-title":"Valence-bond structures: A new proposal","volume":"187","author":"Linnett","year":"1960","journal-title":"Nature"},{"key":"ref_104","first-page":"2643\u22122653","article-title":"A modification of the Lewis-Langmuir octet rule","volume":"83","author":"Linnett","year":"1961","journal-title":"J. Am. Chem. Soc."},{"key":"ref_105","doi-asserted-by":"crossref","unstructured":"Gilli, G., and Gilli, P. (2009). The Nature of the Hydrogen Bond: Outline of a Comprehensive Hydrogen Bond Theory, Oxford University Press.","DOI":"10.1093\/acprof:oso\/9780199558964.001.0001"},{"key":"ref_106","doi-asserted-by":"crossref","first-page":"201","DOI":"10.1021\/cr60156a001","article-title":"The Trans Effect in Complex Inorganic Compounds","volume":"50","author":"Quagliano","year":"1952","journal-title":"Chem. Rev."},{"key":"ref_107","doi-asserted-by":"crossref","first-page":"29742","DOI":"10.1039\/C7CP06393H","article-title":"Hydrogen bonds, and \u03c3-hole and \u03c0-hole bonds\u2013mechanisms protecting doublet and octet electron structures","volume":"19","author":"Grabowski","year":"2017","journal-title":"Phys. Chem. Chem. Phys."},{"key":"ref_108","doi-asserted-by":"crossref","unstructured":"Hoffmann, S.P., Kato, T., Tham, F.S., and Reed, C.A. (2006). Novel weak coordination to silylium ions: Formation of nearly linear Si\u2013H\u2013Si bonds. Chem. Commun., 767\u2013769.","DOI":"10.1039\/b511344j"},{"key":"ref_109","doi-asserted-by":"crossref","first-page":"767","DOI":"10.1071\/CH19557","article-title":"A detailed classification of three-centre two-electron bonds","volume":"73","author":"Gnanasekar","year":"2020","journal-title":"Aust. J. Chem."},{"key":"ref_110","doi-asserted-by":"crossref","first-page":"3","DOI":"10.1016\/S0010-8545(00)80104-6","article-title":"Macrocyclic coordination compounds formed by condensation of metal-amine complexes with aliphatic carbonyl compounds","volume":"3","author":"Curtis","year":"1968","journal-title":"Coord. Chem. Rev."},{"key":"ref_111","doi-asserted-by":"crossref","first-page":"12526","DOI":"10.1021\/acs.inorgchem.2c00921","article-title":"Anion Binding Based on Hg3 Anticrowns as Multidentate Lewis Acidic Hosts","volume":"61","author":"Loveday","year":"2022","journal-title":"Inorg. Chem."},{"key":"ref_112","doi-asserted-by":"crossref","first-page":"8428","DOI":"10.1039\/D0CC02758H","article-title":"Asymmetric [N-I-N]+ Halonium Complexes","volume":"56","author":"Ward","year":"2020","journal-title":"Chem. Commun."},{"key":"ref_113","doi-asserted-by":"crossref","unstructured":"Giannozzi, P., Andreussi, O., Brumme, T., Bunau, O., Nardelli, M.B., Calandra, M., and Baroni, S. (2017). Advanced capabilities for materials modelling with Quantum ESPRESSO. J. Phys. Condens. Matter., 29.","DOI":"10.1088\/1361-648X\/aa8f79"},{"key":"ref_114","doi-asserted-by":"crossref","first-page":"15298","DOI":"10.1039\/D1SC03578A","article-title":"Direct metal\u2013carbon bonding in symmetric bis(C\u2013H) agostic nickel(I) complexes","volume":"12","author":"He","year":"2021","journal-title":"Chem. Sci."},{"key":"ref_115","doi-asserted-by":"crossref","unstructured":"Ruth, A., N\u00e9meth, K., Harkay, K.C., Terdik, J.Z., Spentzouris, L., and Terry, J. (2013). Searching for low-workfunction phases in the Cs-Te system: The case of Cs2Te5. J. Appl. Phys., 113.","DOI":"10.1063\/1.4804155"}],"container-title":["Molecules"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/www.mdpi.com\/1420-3049\/31\/1\/82\/pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,12,26]],"date-time":"2025-12-26T05:17:42Z","timestamp":1766726262000},"score":1,"resource":{"primary":{"URL":"https:\/\/www.mdpi.com\/1420-3049\/31\/1\/82"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2025,12,24]]},"references-count":115,"journal-issue":{"issue":"1","published-online":{"date-parts":[[2026,1]]}},"alternative-id":["molecules31010082"],"URL":"https:\/\/doi.org\/10.3390\/molecules31010082","relation":{},"ISSN":["1420-3049"],"issn-type":[{"value":"1420-3049","type":"electronic"}],"subject":[],"published":{"date-parts":[[2025,12,24]]}}}